Optical films comprising phenyl ethylene (meth)acrylate monomers

ABSTRACT

Presently described are (e.g. microstructured) optical films and polymerizable resin compositions comprising at least one (meth)acrylate monomer comprising an unsubstituted or substituted phenyl ethylene group referred to as phenyl ethylene (meth)acrylate monomers.

Certain microstructured optical products, such as described in U.S.2005/0148725, are commonly referred to as a “brightness enhancingfilms”. Brightness enhancing films are utilized in many electronicproducts to increase the brightness of a backlit flat panel display suchas a liquid crystal display (LCD) including those used inelectroluminescent panels, laptop computer displays, word processors,desktop monitors, televisions, video cameras, as well as automotive andaviation displays.

Brightness enhancing films desirably exhibit specific optical andphysical properties including the index of refraction of a brightnessenhancing film that is related to the brightness gain (i.e. “gain”)produced. Improved brightness can allow the electronic product tooperate more efficiently by using less power to light the display,thereby reducing the power consumption, placing a lower heat load on itscomponents, and extending the lifetime of the product.

Brightness enhancing films have been prepared from polymerizable resincompositions comprising high index of refraction monomers that are curedor polymerized. Halogenated (e.g. brominated) monomers or oligomers areoften employed to attain refractive indices of for example 1.56 orgreater. Another way to attain high refractive index compositions is toemploy a polymerizable composition that comprises high refractive indexnanoparticles.

One common monomer that has been employed as a reactive diluent inpolymerizable resin compositions is phenoxyethyl acrylate, having arefractive index of 1.517 and a viscosity of 12 cps at 25° C.

DETAILED DESCRIPTION

Presently described are (e.g. microstructured) optical films andpolymerizable resin compositions comprising at least one (meth)acrylatemonomer comprising an unsubstituted or substituted phenyl ethylenegroup. Such monomers will be referred to herein as phenyl ethylene(meth)acrylate monomers.

The polymerized microstructure can be an optical element or opticalproduct constructed of a base layer and a polymerized microstructuredoptical layer. The base layer and optical layer can be formed from thesame or different polymeric material. One preferred optical film havinga polymerized microstructured surface is a brightness enhancing film.

Brightness enhancing films generally enhance on-axis luminance (referredherein as “brightness”) of a lighting device. Brightness enhancing filmscan be light transmissible, microstructured films. The microstructuredtopography can be a plurality of prisms on the film surface such thatthe films can be used to redirect light through reflection andrefraction. The height of the prisms typically ranges from about 1 toabout 75 microns. When used in an optical display such as that found inlaptop computers, watches, etc., the microstructured optical film canincrease brightness of an optical display by limiting light escapingfrom the display to within a pair of planes disposed at desired anglesfrom a normal axis running through the optical display. As a result,light that would exit the display outside of the allowable range isreflected back into the display where a portion of it can be “recycled”and returned back to the microstructured film at an angle that allows itto escape from the display. The recycling is useful because it canreduce power consumption needed to provide a display with a desiredlevel of brightness.

The brightness enhancing film of the invention generally comprises a(e.g. preformed polymeric film) base layer and an optical layer. Theoptical layer comprises a linear array of regular right prisms. Eachprism has a first facet and a second facet. The prisms are formed onbase that has a first surface on which the prisms are formed and asecond surface that is substantially flat or planar and opposite firstsurface. By right prisms it is meant that the apex angle is typicallyabout 90°. However, this angle can range from 70° to 120° and may rangefrom 80° to 100°. These apexes can be sharp, rounded or flattened ortruncated. For example, the ridges can be rounded to a radius in a rangeof 4 to 7 to 15 micrometers. The spacing between prism peaks (or pitch)can be 5 to 300 microns. For thin brightness enhancing films, the pitchis preferably 10 to 36 microns, and more preferably 18 to 24 microns.This corresponds to prism heights of preferably about 5 to 18 microns,and more preferably about 9 to 12 microns. The prism facets need not beidentical, and the prisms may be tilted with respect to each other. Therelationship between the total thickness of the optical article, and theheight of the prisms, may vary. However, it is typically desirable touse relatively thinner optical layers with well-defined prism facets.For thin brightness enhancing films on substrates with thicknesses closeto 1 mil (20-35 microns), a typical ratio of prism height to totalthickness is generally between 0.2 and 0.4.

As described in Lu et al., U.S. Pat. No. 5,175,030, and Lu, U.S. Pat.No. 5,183,597, a microstructure-bearing article (e.g. brightnessenhancing film) can be prepared by a method including the steps of (a)preparing a polymerizable composition; (b) depositing the polymerizablecomposition onto a master negative microstructured molding surface in anamount barely sufficient to fill the cavities of the master; (c) fillingthe cavities by moving a bead of the polymerizable composition between apreformed base (such as a PET film) and the master, at least one ofwhich is flexible; and (d) curing the composition. The master can bemetallic, such as nickel, nickel-plated copper or brass, or can be athermoplastic material that is stable under the polymerizationconditions, and that preferably has a surface energy that allows cleanremoval of the polymerized material from the master. One or more thesurfaces of the base film can optionally be primed or otherwise betreated to promote adhesion of the optical layer to the base.

In some embodiments, the polymerizable resin composition comprisessurface modified inorganic nanoparticles. In such embodiments,“polymerizable composition” refers to the total composition, i.e. theorganic component and surface modified inorganic nanoparticles. The“organic component” refers to all of the components of the compositionexcept for the surface modified inorganic nanoparticles. Since thesurface treatments are generally adsorbed or otherwise attached to thesurface of the inorganic nanoparticles, the surface treatments are notconsidered a portion of the bulk organic component. When the compositionis free of inorganic materials such as surface modified inorganicnanoparticles the polymerizable resin composition and organic componentare one in the same.

The organic component as well as the polymerizable composition ispreferably substantially solvent free. “Substantially solvent free”refer to the polymerizable composition having less than 5 wt-%, 4 wt-%,3 wt-%, 2 wt-%, 1 wt-% and 0.5 wt-% of non-polymerizable (e.g. organic)solvent. The concentration of solvent can be determined by knownmethods, such as gas chromatography (as described in ASTM D5403).Solvent concentrations of less than 0.5 wt-% are preferred.

The components of the organic component are preferably chosen such thatthe polymerizable resin composition has a low viscosity. In someembodiments, the viscosity of the organic component is less than 1000cps and typically less than 900 cps at the coating temperature. Theviscosity of the organic component may be less than 800 cps, less than700 cps, less than 600 cps, or less than 500 cps at the coatingtemperature. As used herein, viscosity is measured (at a shear rate upto 1000 sec-1) with 25 mm parallel plates using a Dynamic StressRheometer. Further, the viscosity of the organic component is typicallyat least 10 cps, more typically at least 50 cps at the coatingtemperature.

The coating temperature typically ranges from ambient temperature, 77°F. (25° C.) to 180° F. (82° C.). The coating temperature may be lessthan 170° F. (77° C.), less than 160° F. (71° C.), less than 150° F.(66° C.), less than 140° F. (60° C.), less than 130° F. (54° C.), orless than 120° F. (49° C.). The phenyl ethylene (meth)acrylate monomerand the organic components can be a solid or comprise a solid componentprovided that the melting point in the polymerizable composition is lessthan the coating temperature. The organic component as well as thephenyl ethylene (meth)acrylate monomer described herein is preferably aliquid at ambient temperature.

In some embodiments, the phenyl ethylene (meth)acrylate monomer has aviscosity of less than 80 cps, 70 cps, or 60 cps. Some preferred speciesof phenyl ethylene (meth)acrylate monomer have a viscosity of less than10 cps at 25° C. The phenyl ethylene (meth)acrylate monomer, as well asthe organic component has a refractive index of at least 1.52.Preferably the phenyl ethylene (meth)acrylate monomer has a refractiveindex of at least 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, or 1.60. Thepolymerizable composition including high refractive index nanoparticlescan have a refractive index as high as 1.70. (e.g. at least 1.61, 1.62,1.63, 1.64, 1.65, 1.66, 1.67, 1.68, or 1.69). High transmittance in thevisible light spectrum is also typically preferred.

The polymerizable composition is energy curable in time scalespreferably less than five minutes (e.g. for a brightness enhancing filmhaving a 75 micron thickness). The polymerizable composition ispreferably sufficiently crosslinked to provide a glass transitiontemperature that is typically greater than 45° C. The glass transitiontemperature can be measured by methods known in the art, such asDifferential Scanning calorimetry (DSC), modulated DSC, or DynamicMechanical Analysis. The polymerizable composition can be polymerized byconventional free radical polymerization methods.

The presently described optical films are prepared from a polymerizableresin composition comprising at least one (meth)acrylate monomercomprising a unsubstituted or substituted phenyl ethylene group. The(meth)acrylate substituent is preferably an acrylate substituent.

The phenyl ethylene group of the (meth)acrylate monomer has thefollowing structure:

whereinR is an optional substituent;t ranges from 0 to 5; andR3 is H or a substituent.

In some embodiments, the aromatic ring of the phenyl ethylene group isunsubstituted, i.e. t is 0.

In other embodiments, R is independently selected from a C2-C12 alkylgroup, halogen, alkyaryl, an ether group, and a nitro group. Typically tis 1 or 2.

In some embodiments, both R3 groups are H. In other embodiments, atleast one R3 group comprises a substituent. The substituent is typicallyselected from a C2-C12 alkyl group, halogen, alkyaryl, and an ethergroup.

In some embodiments, t is 0 and both R3 groups are hydrogen.

In some embodiments, the phenyl ethylene (meth)acrylate monomer has thestructure

wherein R is an optional substituent as previously described;R3 is H or a substituent as previously described;L is a C2-C12 alkyl group optionally substituted with one or morehydroxyl groups;n ranges from 0 to 10; and

R1 is H or CH₃.

In other embodiments, the phenyl ethylene (meth)acrylate monomer has thestructure

wherein R is an optional substituent as previously described;R3 is H or a substituent as previously described;R4 is a substituent comprising a (meth)acrylate group, p independentlyranges from 0 to 2 provided at least one p is 1.

Suitable R4 substituents that comprise a (meth)acrylate include forexample

whereinL is a C2-C12 alkyl group optionally substituted with one or morehydroxyl groups;n ranges from 0 to 10; and

R1 is H or CH₃.

Regardless of the structure, in some embodiments, n is preferably atleast 1. Further, L is preferably a C2-C3 alkyl group optionallysubstituted with one or more hydroxyl groups.

Suitable phenyl ethylene (meth)acrylate monomers include for example

The phenyl ethylene (meth)acrylate monomers described herein can beprepared by synthetic methods as known by one of ordinary skill in theart. For example, cinnamyl alcohol or stilbene alcohol can be reactedwith acryloyl chloride. Exemplary syntheses are described in theforthcoming examples. Suitable phenyl ethylene groups derived fromstarting alcohol monomers are set forth in Tables 1 and 2 as follows:

TABLE 1

TABLE 2

The starting materials are commercially available from various suppliersincluding Aldrich, TCI, and VWR.

In some embodiments, the phenyl ethylene monomer the phenyl ethylenemonomer is a multi-(meth)acrylate monomer. The phenyl ethylene monomeris preferably a monofunctional (meth)acrylate monomer. Suchmonofunctional phenyl ethylene monomer is preferably employed incombination with other multi- and in particular di-(meth)acrylatemonomers.

The amount of phenyl ethylene (meth)acrylate employed in thepolymerizable resin composition can vary. A small concentration, forexample 1 wt-%, 2 wt-%, 3 wt-%, 4 wt-%, or 5 wt-% may be substituted fora portion of a lower refractive index component(s) in order to raise therefractive index of the polymerizable resin composition. However,typically the polymerizable resin composition comprises 15 wt-% to 75wt-% of one or more phenyl ethylene (meth)acrylate monomers incombination with 25 wt-% to 75 wt-% of one or more aromatic monomers oroligomers having at least two polymerizable (meth)acrylate groups.

A variety of aromatic monomers and/or oligomers having at least twopolymerizable (meth)acrylate groups may be employed. Such aromaticmonomer typically comprises at least two aromatic rings and a molecularweight of at least 350 g/mole, 400 g/mole, or 450 g/mole.

The aromatic monomer or oligomer having at least two polymerizable(meth)acrylate groups may be synthesized or purchased. The aromaticmonomer or oligomer typically contains a major portion, i.e. at least60-70 wt-%, of a specific structure. It is commonly appreciated thatother reaction products are also typically present as a byproduct of thesynthesis of such monomers.

In some embodiments, the polymerizable composition comprises at leastone phenyl ethylene (meth)acrylate and at least one aromatic (optionallybrominated) difunctional (meth)acrylate monomer that comprises a majorportion having the following general structure:

wherein Z is independently —C(CH₃)₂—, —CH₂—, —C(O)—, —S—, —S(O)—, or—S(O)₂—, each Q is independently O or S. L is a linking group. L mayindependently comprise a branched or linear C₂-C₁₂ alkyl group and nranges from 0 to 10. L preferably comprises a branched or linear C₂-C₆alkyl group. More preferably L is C₂ or C₃ and n is 0, 1, 2 or 3. Thecarbon chain of the alkyl linking group may optionally be substitutedwith one or more hydroxy groups. For example L may be —CH₂CH(OH)CH₂—.Typically, the linking groups are the same. R1 is independently hydrogenor methyl.

In some embodiments, the aromatic monomer is a bisphenoldi(meth)acrylate, i.e. the reaction product of a bisphenol A diglycidylether and acrylic acid. Although bisphenol A diglycidyl ether isgenerally more widely available, it is appreciated that other biphenoldiglycidyl ether such as bisphenol F diglycidyl ether could also beemployed. For example, the di(meth)acrylate monomer can be the reactionproduct of Tetrabromobisphenol A diglycidyl ether and acrylic acid. Suchmonomer may be obtained from UCB Corporation, Smyrna, Ga. under thetrade designation “RDX-51027”. This material comprises a major portionof 2-propenoic acid,(1-methylethylidene)bis[(2,6-dibromo-4,1-phenylene)oxy(2-hydroxy-3,1-propanediyl)]ester.

One exemplary bisphenol-A ethoxylated diacrylate monomer is commerciallyavailable from Sartomer under the trade designations “SR602” (reportedto have a viscosity of 610 cps at 20° C. and a Tg of 2° C.). Anotherexemplary bisphenol-A ethoxylated diacrylate monomer is as commerciallyavailable from Sartomer under the trade designation “SR601” (reported tohave a viscosity of 1080 cps at 20° C. and a Tg of 60° C.).

Alternatively or in addition to, the organic component may comprise oneor more (meth)acrylated aromatic epoxy oligomers. Various(meth)acrylated aromatic epoxy oligomers are commercially available. Forexample, (meth)acrylated aromatic epoxy, (described as a modified epoxyacrylates), are available from Sartomer, Exton, Pa. under the tradedesignation “CN118”, and “CN115”. (Meth)acrylated aromatic epoxyoligomer, (described as an epoxy acrylate oligomer), is available fromSartomer under the trade designation “CN2204”. Further, a(meth)acrylated aromatic epoxy oligomer, (described as an epoxy novolakacrylate blended with 40% trimethylolpropane triacrylate), is availablefrom Sartomer under the trade designation “CN 112C60”. One exemplaryaromatic epoxy acrylate is commercially available from Sartomer underthe trade designation “CN120” (reported by the supplier to have arefractive index of 1.5556, a viscosity of 2150 at 65° C., and a Tg of60° C.).

In some embodiments, the polymerizable resin composition comprises atleast one phenyl ethylene (meth)acrylate (meth)acrylate and at least onedifunctional biphenyl (meth)acrylate monomer that comprises a majorportion having the following general structure:

wherein each R1 is independently H or methyl;each R2 is independently Br;m ranges from 0 to 4;each Q is independently O or S; n ranges from 0 to 10;L is a C2 to C12 alkyl group optionally substituted with one or morehydroxyl groups;z is an aromatic ring; andt is independently 0 or 1.

In some aspects, Q is preferably O. Further, n is typically 0, 1 or 2. Lis typically C₂ or C₃. Alternatively, L is typically a hydroxylsubstituted C₂ or C₃. In some embodiments, z is preferably fused to thephenyl group thereby forming a binapthyl core structure.

Preferably, at least one of the -Q[L-O]n C(O)C(R1)═CH₂ groups issubstituted at the ortho or meta position. More preferably, the biphenyldi(meth)acrylate monomer comprises a sufficient amount of ortho and/ormeta (meth)acrylate substituents such that the monomer is a liquid at25° C. In some embodiments, each (meth)acrylate group containingsubstituent is bonded to an aromatic ring group at an ortho or metaposition. It is preferred that the biphenyl di(meth)acrylate monomercomprises a major amount of ortho (meth)acrylate substituents (i.e. atleast 50%, 60%, 70%, 80%, 90%, or 95% of the substituents of thebiphenyl di(meth)acrylate monomer). In some embodiments, each(meth)acrylate group containing substituent is bonded to an aromaticring group at an ortho or meta position. As the number of meta- andparticularly para-substituents increases, the viscosity of the organiccomponents can increase as well. Further, para-biphenyl di(meth)acrylatemonomers are solids at room temperature, with little solubility (i.e.less than 10%), even in phenoxyethyl acrylate and tetrahydrofurfurylacrylate.

Such biphenyl monomers are described in further detail in Published U.S.Application No. 2008/0221291. Other biphenyl di(meth)acrylate monomerare described in the literature.

The polymerizable resin composition may optionally comprise one or moremonofunctional diluents in amounts up to about 50 wt-%. In someembodiments, the polymerizable resin composition comprises at least 5wt-%, 10 wt-% or 15 wt-% of such monofunctional diluents to improve theprocessability of the resin composition by reducing its viscosity.

Aromatic (e.g. monofunctional) (meth)acrylate monomers typicallycomprise a phenyl, cumyl, biphenyl, or napthyl group. Preferred diluentscan have a refractive index greater than 1.50, 1.51, 1.52, 1.53, 1.54,or 1.55. Such reactive diluents can be halogenated, non-brominated, ornon-halogenated.

Suitable monomers include phenoxyethyl (meth)acrylate;phenoxy-2-methylethyl (meth)acrylate; phenoxyethoxyethyl (meth)acrylate,3-hydroxy-2-hydroxypropyl (meth)acrylate; benzyl (meth)acrylate;phenylthio ethyl acrylate; 2-naphthylthio ethyl acrylate; 1-naphthylthioethyl acrylate; naphthyloxy ethyl acrylate; 2-naphthyloxy ethylacrylate; phenoxy 2-methylethyl acrylate; phenoxyethoxyethyl acrylate;3-phenoxy-2-hydroxy propyl acrylate; and phenyl acrylate.

Phenoxyethyl acrylate is commercially available from more than onesource including from Sartomer under the trade designation “SR339”; fromEternal Chemical Co. Ltd. under the trade designation “Etermer 210”; andfrom Toagosei Co. Ltd under the trade designation “TO-1166”. Phenylthioethyl acrylate (PTEA) is also commerically available from Cognis. Thestructure of these monomers is shown as follows:

In some embodiments, the polymerizable compositions comprise one or moremonofunctional biphenyl monomer(s).

Monofunctional biphenyl monomers comprise a terminal biphenyl group(wherein the two phenyl groups are not fused, but joined by a bond) or aterminal group comprising two aromatic groups joined by a linking group(e.g. Q). For example, when the linking group is methane, the terminalgroup is a biphenylmethane group. Alternatively, wherein the linkinggroup is —(C(CH₃)₂—, the terminal group is 4-cumyl phenyl. Themonofunctional biphenyl monomer(s) also comprise a single ethylenicallyunsaturated group that is preferably polymerizable by exposure to (e.g.UV) radiation. The monofunctional biphenyl monomer(s) preferablycomprise a single (meth)acrylate group or single thio(meth)acrylategroup. Acrylate functionality is typically preferred. In some aspects,the biphenyl group is joined directly to the ethylenically unsaturated(e.g. (meth)acrylate) group. An exemplary monomer of this type is2-phenyl-phenyl acrylate. The biphenyl mono(meth)acrylate or biphenylthio(meth)acrylate monomer may further comprise a (e.g. 1 to 5 carbon)alkyl group optionally substituted with one or more hydroxyl groups. Anexemplary species of this type is 2-phenyl-2-phenoxyethyl acrylate.

In one embodiment, a monofunctional biphenyl (meth)acrylate monomer isemployed having the general structure:

wherein R1 is H or CH₃;

Q is O or S;

n ranges from 0 to 10 (e.g. n is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10); and

L is preferably an alkyl group having 1 to 5 carbon atoms (i.e. methyl,ethyl, propyl, butyl, or pentyl), optionally substituted with hydroxy.

In another embodiment, the monofunctional biphenyl (meth)acrylatemonomer has the general structure:

wherein R1 is H or CH₃;

Q is O or S;

Z is selected from —(C(CH₃)₂—, —CH₂, —C(O)—, —S(O)—, and —S(O)₂—;

n ranges from 0 to 10 (e.g. n is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10); and

L is an alkyl group having 1 to 5 carbon atoms (i.e. methyl, ethyl,butyl, or pentyl), optionally substituted with hydroxy.

Some specific monomers that are commercially available from Toagosei Co.Ltd. of Japan, include for example 2-phenyl-phenyl acrylate availableunder the trade designation “TO-2344”, 4-(-2-phenyl-2-propyl)phenylacrylate available under the trade designation “TO-2345”, and2-phenyl-2-phenoxyethyl acrylate, available under the trade designation“TO-1463”.

Various combinations of aromatic monofunctional (meth)acrylate monomerscan be employed. For example, a (meth)acrylate monomer comprising aphenyl group may be employed in combination with one or more(meth)acrylate monomers comprising a biphenyl group. Further, twodifferent biphenyl (meth)acrylate monofunctional monomers may beemployed.

The polymerizable resin may optionally comprise up to 35 wt-% of variousother (e.g. non-halogenated) ethylenically unsaturated monomers. Forexample, when the (e.g. prism) structures are cast and photocured upon apolycarbonate preformed polymeric film the polymerizable resincomposition may comprise one or more N,N-disubstituted (meth)acrylamidemonomers. These include N-alkylacrylamides and N,N-dialkylacrylamides,especially those containing C₁₋₄ alkyl groups. Examples areN-isopropylacrylamide, N-t-butylacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, N-vinyl pyrrolidone and N-vinyl caprolactam.

The polymerizable resin composition may also optionally comprise up to20 wt-% of a non-aromatic crosslinker that comprises at least three(meth)acrylate groups. Suitable crosslinking agents include for examplepentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,trimethylolpropane tri(methacrylate), dipentaerythritolpenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate,trimethylolpropane ethoxylate tri(meth)acrylate, glyceryltri(meth)acrylate, pentaerythritol propoxylate tri(meth)acrylate, andditrimethylolpropane tetra(meth)acrylate. Any one or combination ofcrosslinking agents may be employed. Since methacrylate groups tend tobe less reactive than acrylate groups, the crosslinker(s) are preferablyfree of methacrylate functionality.

Various crosslinkers are commercially available. For example,pentaerythritol triacrylate (PETA) is commercially available fromSartomer Company, Exton, Pa. under the trade designation “SR444”; fromOsaka Organic Chemical Industry, Ltd. Osaka, Japan under the tradedesignation “Viscoat #300”; from Toagosei Co. Ltd., Tokyo, Japan underthe trade designation “Aronix M-305”; and from Eternal Chemical Co.,Ltd., Kaohsiung, Taiwan under the trade designation “Etermer 235”.Trimethylol propane triacrylate (TMPTA) is commercially available fromSartomer Company under the trade designations “SR351”. TMPTA is alsoavailable from Toagosei Co. Ltd. under the trade designation “AronixM-309”. Further, ethoxylated trimethylolpropane triacrylate andethoxylated pentaerythritol triacrylate are commercially available fromSartomer under the trade designations “SR454” and “SR494” respectively.

In some embodiments, it is preferred that the polymerizedmicrostructured surface of the optical film, the polymerizable resincomposition, and the phenyl ethylene (meth)acrylate monomer aresubstantially free (i.e. contain less than 1 wt-%) of bromine. In otherembodiments, the total amount of bromine in combination with chlorine isless than 1 wt-%. In some aspects, the polymerized microstructuredsurface or the optical film, the polymerizable resin composition, andthe phenyl ethylene (meth)acrylate monomer are substantiallynon-halogenated (i.e. contains less than 1 wt-% total of bromine,chlorine, fluorine and iodine).

The UV curable polymerizable compositions comprise at least onephotoinitiator. A single photoinitiator or blends thereof may beemployed in the brightness enhancement film of the invention. In generalthe photoinitiator(s) are at least partially soluble (e.g. at theprocessing temperature of the resin) and substantially colorless afterbeing polymerized. The photoinitiator may be (e.g. yellow) colored,provided that the photoinitiator is rendered substantially colorlessafter exposure to the UV light source.

Suitable photoinitiators include monoacylphosphine oxide andbisacylphosphine oxide. Commercially available mono or bisacylphosphineoxide photoinitiators include 2,4,6-trimethylbenzoybiphenylphosphineoxide, commercially available from BASF (Charlotte, N.C.) under thetrade designation “Lucirin TPO”; ethyl-2,4,6-trimethylbenzoylphenylphosphinate, also commercially available from BASF under the tradedesignation “Lucirin TPO-L”; andbis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide commercially availablefrom Ciba Specialty Chemicals under the trade designation “Irgacure819”. Other suitable photoinitiators include2-hydroxy-2-methyl-1-phenyl-propan-1-one, commercially available fromCiba Specialty Chemicals under the trade designation “Darocur 1173” aswell as other photoinitiators commercially available from Ciba SpecialtyChemicals under the trade designations “Darocur 4265”, “Irgacure 651”,“Irgacure 1800”, “Irgacure 369”, “Irgacure 1700”, and “Irgacure 907”.

The photoinitiator can be used at a concentration of about 0.1 to about10 weight percent. More preferably, the photoinitiator is used at aconcentration of about 0.5 to about 5 wt-%. Greater than 5 wt-% isgenerally disadvantageous in view of the tendency to cause yellowdiscoloration of the brightness enhancing film. Other photoinitiatorsand photoinitiator may also suitably be employed as may be determined byone of ordinary skill in the art.

Surfactants such as fluorosurfactants and silicone based surfactants canoptionally be included in the polymerizable composition to reducesurface tension, improve wetting, allow smoother coating and fewerdefects of the coating, etc.

The phenyl ethylene (meth)acrylate monomers described herein areparticularly useful in preparing non-halogenated high refractive indexpolymerizable organic compositions. In some aspects the compositions arefree of inorganic nanoparticles.

In other embodiments, the polymerizable composition further comprisesinorganic nanoparticles.

Surface modified (e.g. colloidal) nanoparticles can be present in thepolymerized structure in an amount effective to enhance the durabilityand/or refractive index of the article or optical element. In someembodiments, the total amount of surface modified inorganicnanoparticles can be present in the polymerizable resin or opticalarticle in an amount of at least 10 wt-%, 20 wt-%, 30 wt-% or 40 wt-%.The concentration is typically less than to 70 wt-%, and more typicallyless than 60 wt-% in order that the polymerizable resin composition hasa suitable viscosity for use in cast and cure processes of makingmicrostructured films.

The size of such particles is chosen to avoid significant visible lightscattering. It may be desirable to employ a mixture of inorganic oxideparticle types to optimize an optical or material property and to lowertotal composition cost. The surface modified colloidal nanoparticles canbe oxide particles having a (e.g. unassociated) primary particle size orassociated particle size of greater than 1 nm, 5 nm or 10 nm. Theprimary or associated particle size is generally and less than 100 nm,75 nm, or 50 nm. Typically the primary or associated particle size isless than 40 nm, 30 nm, or 20 nm. It is preferred that the nanoparticlesare unassociated. Their measurements can be based on transmissionelectron microscopy (TEM). The nanoparticles can include metal oxidessuch as, for example, alumina, zirconia, titania, mixtures thereof, ormixed oxides thereof. Surface modified colloidal nanoparticles can besubstantially fully condensed.

Fully condensed nanoparticles (with the exception of silica) typicallyhave a degree of crystallinity (measured as isolated metal oxideparticles) greater than 55%, preferably greater than 60%, and morepreferably greater than 70%. For example, the degree of crystallinitycan range up to about 86% or greater. The degree of crystallinity can bedetermined by X-ray diffraction techniques. Condensed crystalline (e.g.zirconia) nanoparticles have a high refractive index whereas amorphousnanoparticles typically have a lower refractive index.

Zirconia and titania nanoparticles can have a particle size from 5 to 50nm, or 5 to 15 nm, or 8 nm to 12 nm. Zirconia nanoparticles can bepresent in the durable article or optical element in an amount from 10to 70 wt-%, or 30 to 60 wt-%. Zirconias for use in composition andarticles of the invention are available from Nalco Chemical Co. underthe trade designation “Nalco OOSSOO8” and from Buhler AG Uzwil,Switzerland under the trade designation “Buhler zirconia Z—WO sol”.

The zirconia particles can be prepared using hydrothermal technology asdescribed in U.S. Pat. No. 7,241,437. The nanoparticles are surfacemodified. Surface modification involves attaching surface modificationagents to inorganic oxide (e.g. zirconia) particles to modify thesurface characteristics. The overall objective of the surfacemodification of the inorganic particles is to provide resins withhomogeneous components and preferably a low viscosity that can beprepared into films (e.g. using cast and cure processes) with highbrightness.

The nanoparticles are often surface-modified to improve compatibilitywith the organic matrix material. The surface-modified nanoparticles areoften non-associated, non-agglomerated, or a combination thereof in anorganic matrix material. The resulting light management films thatcontain these surface-modified nanoparticles tend to have high opticalclarity and low haze. The addition of the high refractive indexsurface-modified nanoparticles, such as zirconia, can increase the gainof brightness enhancement film compared to films that contain onlypolymerized organic material.

The monocarboxylic acid surface treatments preferably comprise acompatibilizing group. The monocarboxylic acids may be represented bythe formula A-B where the A group is a (e.g. monocarboxylic acid) groupcapable of attaching to the surface of a (e.g. zirconia or titania)nanoparticle, and B is a compatibilizing group that comprises a varietyof different functionalities. The carboxylic acid group can be attachedto the surface by adsorption and/or formation of an ionic bond. Thecompatibilizing group B is generally chosen such that it is compatiblewith the polymerizable resin of the (e.g. brightness enhancing) opticalarticle. The compatibilizing group B can be reactive or nonreactive andcan be polar or non-polar.

Compatibilizing groups B that can impart non-polar character to thezirconia particles include, for example, linear or branched aromatic oraliphatic hydrocarbons. Representative examples of non-polar modifyingagents having carboxylic acid functionality include octanoic acid,dodecanoic acid, stearic acid, oleic acid, and combinations thereof.

The compatibilizing group B may optionally be reactive such that it cancopolymerize with the organic matrix of the (e.g. brightness enhancing)optical article. For instance, free radically polymerizable groups suchas (meth)acrylate compatibilizing groups can copolymerize with(meth)acrylate functional organic monomers to generate brightnessenhancement articles with good homogeneity.

Suitable surface modifications are described in U.S. Publication No.2007/0112097 and WO2008/121465.

The surface modified particles can be incorporated into the curable(i.e. polymerizable) resin compositions in various methods. In apreferred aspect, a solvent exchange procedure is utilized whereby theresin is added to the surface modified sol, followed by removal of thewater and co-solvent (if used) via evaporation, thus leaving theparticles dispersed in the polymerizable resin. The evaporation step canbe accomplished for example, via distillation, rotary evaporation oroven drying. In another aspect, the surface modified particles can beextracted into a water immiscible solvent followed by solvent exchange,if so desired. Alternatively, another method for incorporating thesurface modified nanoparticles in the polymerizable resin involves thedrying of the modified particles into a powder, followed by the additionof the resin material into which the particles are dispersed. The dryingstep in this method can be accomplished by conventional means suitablefor the system, such as, for example, oven drying or spray drying.

The optical layer can directly contact the base layer or be opticallyaligned to the base layer, and can be of a size, shape and thicknessallowing the optical layer to direct or concentrate the flow of light.The optical layer can have a structured or micro-structured surface thatcan have any of a number of useful patterns such as described and shownin the U.S. Pat. No. 7,074,463. The micro-structured surface can be aplurality of parallel longitudinal ridges extending along a length orwidth of the film. These ridges can be formed from a plurality of prismapexes. These apexes can be sharp, rounded or flattened or truncated.For example, the ridges can be rounded to a radius in a range of 4 to 7to 15 micrometers.

These include regular or irregular prismatic patterns, which can be anannular prismatic pattern, a cube-corner pattern or any other lenticularmicrostructure. A useful microstructure is a regular prismatic patternthat can act as a totally internal reflecting film for use as abrightness enhancement film. Another useful microstructure is acorner-cube prismatic pattern that can act as a retro-reflecting film orelement for use as reflecting film. Another useful microstructure is aprismatic pattern that can act as an optical element for use in anoptical display. Another useful microstructure is a prismatic patternthat can act as an optical turning film or element for use in an opticaldisplay.

The base layer can be of a nature and composition suitable for use in anoptical product, i.e. a product designed to control the flow of light.Almost any material can be used as a base material as long as thematerial is sufficiently optically clear and is structurally strongenough to be assembled into or used within a particular optical product.A base material can be chosen that has sufficient resistance totemperature and aging that performance of the optical product is notcompromised over time.

Useful base materials include, for example, styrene-acrylonitrile,cellulose acetate butyrate, cellulose acetate propionate, cellulosetriacetate, polyether sulfone, polymethyl methacrylate, polyurethane,polyester, polycarbonate, polyvinyl chloride, polystyrene, polyethylenenaphthalate, copolymers or blends based on naphthalene dicarboxylicacids, polycyclo-olefins, polyimides, and glass. Optionally, the basematerial can contain mixtures or combinations of these materials. In anembodiment, the base may be multi-layered or may contain a dispersedcomponent suspended or dispersed in a continuous phase.

For some optical products such as microstructure-bearing products suchas, for example, brightness enhancement films, examples of preferredbase materials include polyethylene terephthalate (PET) andpolycarbonate. Examples of useful PET films include photogradepolyethylene terephthalate and MELINEX™ PET available from DuPont Filmsof Wilmington, Del.

Some base materials can be optically active, and can act as polarizingmaterials. A number of bases, also referred to herein as films orsubstrates, are known in the optical product art to be useful aspolarizing materials. Polarization of light through a film can beaccomplished, for example, by the inclusion of dichroic polarizers in afilm material that selectively absorbs passing light. Light polarizationcan also be achieved by including inorganic materials such as alignedmica chips or by a discontinuous phase dispersed within a continuousfilm, such as droplets of light modulating liquid crystals dispersedwithin a continuous film. As an alternative, a film can be prepared frommicrofine layers of different materials. The polarizing materials withinthe film can be aligned into a polarizing orientation, for example, byemploying methods such as stretching the film, applying electric ormagnetic fields, and coating techniques.

Examples of polarizing films include those described in U.S. Pat. Nos.5,825,543 and 5,783,120. The use of these polarizer films in combinationwith a brightness enhancement film has been described in U.S. Pat. No.6,111,696.

A second example of a polarizing film that can be used as a base arethose films described in U.S. Pat. No. 5,882,774. Films availablecommercially are the multilayer films sold under the trade designationDBEF (Dual Brightness Enhancement Film) from 3M. The use of suchmultilayer polarizing optical film in a brightness enhancement film hasbeen described in U.S. Pat. No. 5,828,488.

A common way of measuring the effectiveness of such recycling of lightis to measure the gain of an optical film. As used herein, “relativegain”, is defined as the on-axis luminance, as measured by the testmethod described in the examples, when an optical film (or optical filmassembly) is placed on top of the light box, relative to the on-axisluminance measured when no optical film is present on top of the lightbox. This definition can be summarized by the following relationship:

Relative Gain=(Luminance measured with optical film)/(Luminance measuredwithout optical film)

In one embodiment, an optical film comprising a light transmissive (e.g.cured) polymeric material having a microstructured surface is described.The optical film is a substantially non-polarizing film having a singlesheet relative gain of at least 1.60. The relative single sheet gain istypically no greater than 2.05. Accordingly, the single sheet relativegain may also range from any values in the set of relative gain valuesincluding 1.65, 1.70, 1.75, 1.80, 1.85, and 1.90 or greater.

In other embodiments, the inventions relate to various assemblies thatcomprise or consist of two or more films. Each assembly includes a firstmicrostructured optical film proximate a second (e.g. microstructured orunstructured) optical film.

By proximate, it is meant sufficiently near. Proximate can include thefirst microstructured optical film being in contact with the secondoptical film such as by the films merely being stacked together or thefilms may be attached by various means. The films may be attached bymechanical means, chemical means, thermal means, or a combinationthereof. Chemical means includes various pressure sensitive,solvent-based, and hot melt adhesives as well as two-part curableadhesive compositions that crosslink upon exposure to heat, moisture, orradiation. Thermal means includes for example a heated embossed roller,radio frequency (RF) welding, and ultrasonic welding. The optical filmsmay be attached (e.g. continuously) across the entire plane of thefilms, at only select points, or at only the edges. Alternatively, theproximate optical films may be separated from each other with an airinterface. The air interface may be created by increasing the thicknessof either or both optical films at the periphery, such as by applicationof an adhesive. When the films are stacked rather than laminatedtogether, the air interface between the optical films may be only a fewmicrons.

In some embodiments, a first microstructured optical film is proximate asecond microstructured optical film. In such assemblies, themicrostructured surface of the bottom film is preferably disposedproximate the unstructured surface of the top film. For embodiments thatemploy prismatic microstructured films, the prisms of the films aregenerally aligned parallel in one principal direction, the prisms beingseparated by grooves. It is generally preferred to align the prisms (orgrooves) of the second (e.g. bottom) microstructured optical film in astack such that the prisms are substantially orthogonal to the prisms ofthe first (e.g. top) film. However, other alignments can also beemployed. For example, the prisms of the second optical film may bepositioned relative to the prisms of the second optical film such thatthe intersection of grooves or prisms form angles ranging from about 70°to about 120°.

In one embodied assembly, a first microstructured substantiallynon-polarizing optical film is proximate a second microstructuredsubstantially non-polarizing optical film. The gain of this assembly isat least 2.50. The first optical film may be the same as or differentthan the second optical film. For example, the second film may have adifferent base layer composition, a different microstructured surfacecomposition, and/or may have a different surface microstructure. Therelative gain of this assembly is typically less than 3.32. Accordingly,the relative gain of such assembly may also range from any values in theset of relative gain values including 2.55, 2.60, 2.65, 2.70, 2.75,2.80, 2.85, 2.90, 2.95, and 3.00 or greater.

For the following defined terms, these definitions shall be applied,unless a different definition is given in the claims or elsewhere inthis specification.

The term “microstructure” is used herein as defined and explained inU.S. Pat. No. 4,576,850. Thus, it means the configuration of a surfacethat depicts or characterizes the predetermined desired utilitarianpurpose or function of the article having the microstructure.Discontinuities such as projections and indentations in the surface ofsaid article will deviate in profile from the average center line drawnthrough the microstructure such that the sum of the areas embraced bythe surface profile above the center line is equal to the sum of theareas below the line, said line being essentially parallel to thenominal surface (bearing the microstructure) of the article. The heightsof said deviations will typically be about +/−0.005 to +/−750 microns,as measured by an optical or electron microscope, through arepresentative characteristic length of the surface, e.g., 1-30 cm. Saidaverage center line can be piano, concave, convex, aspheric orcombinations thereof. Articles where said deviations are of low order,e.g., from +/−0.005 +/−0.1 or, preferably, +/−0.05 microns, and saiddeviations are of infrequent or minimal occurrence, i.e., the surface isfree of any significant discontinuities, are those where themicrostructure-bearing surface is an essentially “flat” or “smooth”surface, such articles being useful, for example, as precision opticalelements or elements with a precision optical interface, such asophthalmic lenses. Articles where said deviations are of low order andof frequent occurrence include those having anti-reflectivemicrostructure. Articles where said deviations are of high-order, e.g.,from +/−0.1 to +/−750 microns, and attributable to microstructurecomprising a plurality of utilitarian discontinuities which are the sameor different and spaced apart or contiguous in a random or orderedmanner, are articles such as retroreflective cube-corner sheeting,linear Fresnel lenses, video discs and brightness enhancing films. Themicrostructure-bearing surface can contain utilitarian discontinuitiesof both said low and high orders. The microstructure-bearing surface maycontain extraneous or non-utilitarian discontinuities so long as theamounts or types thereof do not significantly interfere with oradversely affect the predetermined desired utilities of said articles.

“Index of refraction,” or “refractive index,” refers to the absoluterefractive index of a material (e.g., a monomer) that is understood tobe the ratio of the speed of electromagnetic radiation in free space tothe speed of the radiation in that material. The refractive index can bemeasured using known methods and is generally measured using an Abberefractometer or Bausch and Lomb Refractometer (CAT No. 33.46.10) in thevisible light region (available commercially, for example, from FisherInstruments of Pittsburgh, Pa.). It is generally appreciated that themeasured index of refraction can vary to some extent depending on theinstrument.“(Meth)acrylate” refers to both acrylate and methacrylate compounds.The term “nanoparticles” is defined herein to mean particles (primaryparticles or associated primary particles) with a diameter less thanabout 100 nm.“Surface modified colloidal nanoparticle” refers to nanoparticles eachwith a modified surface such that the nanoparticles provide a stabledispersion.The recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, and 5).As used in this specification and the appended claims, the singularforms “a”, “an”, and “the” include plural referents unless the contentclearly dictates otherwise. Thus, for example, reference to acomposition containing “a compound” includes a mixture of two or morecompounds. As used in this specification and the appended claims, theterm “or” is generally employed in its sense including “and/or” unlessthe content clearly dictates otherwise.Unless otherwise indicated, all numbers expressing quantities ofingredients, measurement of properties and so forth used in thespecification and claims are to be understood as being modified in allinstances by the term “about.”The present invention should not be considered limited to the particularexamples described herein, but rather should be understood to cover allaspects of the invention as fairly set out in the attached claims.Various modifications, equivalent processes, as well as numerousstructures to which the present invention can be applicable will bereadily apparent to those of skill in the art to which the presentinvention is directed upon review of the instant specification.

EXAMPLES Synthesis of trans-Stilbene-4-oxyacrylate (SA-1)

To a 500 ml round bottom equipped with an overhead stirrer andtemperature probe was added trans-4-hydroxystilbene 23 g (0.117 moles,1.0 equivalents), 4-hydroxy TEMPO 0.01 g, ethyl acetate 350 g, andacryloyl chloride 11.6 g (0.13 moles, 1.1 equivalents). The reaction wascooled to −6C with isopropanol/ice bath and added 50% sodium hydroxide11.25 g (0.14 moles, 1.2 equivalents) slowly keeping the temp below OC.The reaction was sampled after 30 min post addition. The GC indicated 0%starting material and 99% product. While continuing to cool at −5C,added 100 g deionized water, 5 g acetic acid, mixed vigorously for 30minutes. The aqueous was separated and the organic washed with 100 gsaturated sodium carbonate water mixed for 30 minutes, separated and theorganic was concentrated invacuo to recover an off white solid which wasrecrystallized from 100 ml ethyl acetate to recover 19 g (65%) whitepowder. Mp=125-127 Proton NMR indicated clean product. The material wasfound to have a surprisingly high refractive index of 1.657.

Cinnamyl acrylate has the following structure:

Polymerizable Resin Composition 1: 24 parts of cinnamyl acrylate (fromMonomer-Polymer & Dajac Labs, Inc., Feasterville, Pa., having arefractive index of 1.552 and a viscosity of 6 cps at 25° C.), 76 partsCN120 (epoxy acrylate available from Sartomer Company, Exton, Pa.,reported by Sartomer to have a viscosity of 2150 cps at 65° C., arefractive index of 1.5556 and a Tg of 60° C.), 2 parts Darocur 4265(available from Ciba Specialty Chemicals, Tarrytown, N.Y.), and 1 partIrgacure 819 (available from Ciba Specialty Chemicals) were mixedtogether thoroughly in an amber jar.Comparative Polymerizable Resin Composition A: 75 parts CN120, 25 partsSR339 (2-phenoxyethyl acrylate available from Sartomer Company, Exton,Pa., reported by Sartomer to have a viscosity of 12 cps at 25° C., arefractive index of 1.516 and a Tg of 5° C.), and 0.3 parts Darocur 4265(available from Ciba Specialty Chemicals, Tarrytown, N.Y.) were mixedtogether thoroughly in an amber jar.Polymerizable Resin Composition 2: 15 parts of SA-1 (with a refractiveindex of 1.657), 55 parts CN120, 30 parts SR339 (2-phenoxyethyl acrylateavailable from Sartomer Company, Exton, Pa., reported by Sartomer tohave a viscosity of 12 cps at 25° C., a refractive index of 1.516 and aTg of 5° C.), 2 parts Darocur 4265 (available from Ciba SpecialtyChemicals, Tarrytown, N.Y.), and 1 part Irgacure 819 (available fromCiba Specialty Chemicals) were heated and mixed together thoroughly inan amber jar.Comparative Polymerizable Resin Composition B: 65 parts CN 120, 35 partsSR339 (2-phenoxyethyl acrylate available from Sartomer Company, Exton,Pa., reported by Sartomer to have a viscosity of 12 cps at 25° C., arefractive index of 1.516 and a Tg of 5° C.), 2 parts Darocur 4265(available from Ciba Specialty Chemicals, Tarrytown, N.Y.), and 1 partIrgacure 819 (available from Ciba Specialty Chemicals) were mixedtogether thoroughly in an amber jar.

Optical Film Sample Preparation

About 3 grams of warm resin was applied to a 2 mil primed PET(polyester) film, available from DuPont under the trade designation“Melinex 623” and placed against a microstructured tool with a 90/24pattern similar to the commercially available Vikuiti TBEF-90/24. ThePET, resin and tool were passed through a heated laminator set atapproximately 150° F. to create a uniformly thick sample. The toolcontaining the film and coated resin sample was passed at 50 fpm througha Fusion UV processor containing two 600 W/10 in D-bulbs to cure thefilm. The PET and cured resin were removed from the tool and cut intosamples. The test methods used to evaluate the films are as follows:

Gain Test Method

Optical performance of the films was measured using a SpectraScan™PR-650 SpectraColorimeter with an MS-75 lens, available from PhotoResearch, Inc, Chatsworth, Calif. The films were placed on top of adiffusely transmissive hollow light box. The diffuse transmission andreflection of the light box can be described as Lambertian. The lightbox was a six-sided hollow cube measuring approximately 12.5 cm×12.5cm×11.5 cm (L×W×H) made from diffuse PTFE plates of ˜6 mm thickness. Oneface of the box is chosen as the sample surface. The hollow light boxhad a diffuse reflectance of ˜0.83 measured at the sample surface (e.g.˜83%, averaged over the 400-700 nm wavelength range, measurement methoddescribed below). During the gain test, the box is illuminated fromwithin through a ˜1 cm circular hole in the bottom of the box (oppositethe sample surface, with the light directed towards the sample surfacefrom the inside). This illumination is provided using a stabilizedbroadband incandescent light source attached to a fiber-optic bundleused to direct the light (Fostec DCR-11 with ˜1 cm diameter fiber bundleextension from Schott-Fostec LLC, Marlborough Mass. and Auburn, N.Y.). Astandard linear absorbing polarizer (such as Melles Griot 03 FPG 007) isplaced between the sample box and the camera. The camera is focused onthe sample surface of the light box at a distance of ˜0.34 cm and theabsorbing polarizer is placed ˜2.5 cm from the camera lens. Theluminance of the illuminated light box, measured with the polarizer inplace and no sample films, was >150 cd/m². The sample luminance ismeasured with the PR-650 at normal incidence to the plane of the boxsample surface when the sample films are placed parallel to the boxsample surface, the sample films being in general contact with the box.The relative gain is calculated by comparing this sample luminance tothe luminance measured in the same manner from the light box alone. Theentire measurement was carried out in a black enclosure to eliminatestray light sources.

The diffuse reflectance of the light box was measured using a 15.25 cm(6 inch) diameter Spectralon-coated integrating sphere, a stabilizedbroadband halogen light source, and a power supply for the light sourceall supplied by Labsphere (Sutton, N.H.). The integrating sphere hadthree opening ports, one port for the input light (of 2.5 cm diameter),one at 90 degrees along a second axis as the detector port (of 2.5 cmdiameter), and the third at 90 degrees along a third axis (i.e.orthogonal to the first two axes) as the sample port (of 5 cm diameter).A PR-650 Spectracolorimeter (same as above) was focused on the detectorport at a distance of ˜38 cm. The reflective efficiency of theintegrating sphere was calculated using a calibrated reflectancestandard from Labsphere having ˜99% diffuse reflectance (SRT-99-050).The standard was calibrated by Labsphere and traceable to a NISTstandard (SRS-99-020-REFL-51). The reflective efficiency of theintegrating sphere was calculated as follows:

Sphere brightness ratio=1/(1−Rsphere*Rstandard)

The sphere brightness ratio in this case is the ratio of the luminancemeasured at the detector port with the reference sample covering thesample port divided by the luminance measured at the detector port withno sample covering the sample port. Knowing this brightness ratio andthe reflectance of the calibrated standard (Rstandard), the reflectiveefficiency of the integrating sphere, Rsphere, can be calculated. Thisvalue is then used again in a similar equation to measure a sample'sreflectance, in this case the PTFE light box:

Sphere brightness ratio=1/(1-Rsphere*Rsample)

Here the sphere brightness ratio is measured as the ratio of theluminance at the detector with the sample at the sample port divided bythe luminance measured without the sample. Since Rsphere is known fromabove, Rsample can be calculated. These reflectances were calculated at4 nm wavelength intervals and reported as averages over the 400-700 nmwavelength range.The single sheet gain is tested in the vertical (or perpendicularorientation relative to the front face of the diffuser boxed used in theE.T. Tester). In the horizontal, or crossed sheet configuration, thebottom sheet of the film stack is in the vertical orientation and thetop sheet is horizontal or parallel to the front face of the diffuserbox.Table 3 as follows depicts the test results of the optical films.

TABLE 3 Polymerizable Resin ET Gain Single ET Gain crossed - CompositionSheet Sheet 1 1.62 2.56 2 1.63 2.56 Comp-A 1.60 2.51 Comp-B 1.60 2.51

1. An optical film wherein the film comprises a polymerizedmicrostructured surface comprising the reaction product of apolymerizable resin composition comprising at least one (meth)acrylatemonomer comprising a phenyl ethylene group.
 2. (canceled)
 3. The opticalfilm according to claim 1 wherein the (meth)acrylate monomer has arefractive index of at least 1.54.
 4. The optical film according toclaim 1 wherein the (meth)acrylate monomer has a refractive index of atleast 1.60.
 5. The optical film according to claim 1 wherein the(meth)acrylate monomer has a viscosity of less than 100 cps at 25° C. 6.The optical film of claim 1 wherein the (meth)acrylate monomer has thestructure

wherein R is an optional substituent; t ranges from 0 to 5; R3 is H or asubstituent; L is a C2-C12 alkyl group optionally substituted with oneor more hydroxyl groups; n ranges from 0 to 10; and R1 is H or CH₃. 7.The optical film of claim 6 wherein t is
 0. 8. The optical film of claim6 wherein R3 is H.
 9. The optical film of claim 6 wherein R3 isindependently selected from a C2-C12 alkyl group, halogen, alkyaryl, anether group, and a nitro group.
 10. The optical film of claim 6 whereinn is
 0. 11. The optical film of claim 1 wherein the (meth)acrylatemonomer has the structure

wherein R4 is a substituent comprising a (meth)acrylate group, pindependently ranges from 0 to 2 provided one p is at least 1; R is anoptional substituent; t ranges from 0 to 5; and R3 is H or asubstituent.
 12. The optical film of claim 11 wherein t is
 0. 13. Theoptical film of claim 11 wherein R3 is H.
 14. The optical film of claim11 wherein R3 is independently selected from a C2-C12 alkyl, a halogen,and an ether group.
 15. The optical film of claim 11 wherein R4 isselected from the group consisting of

wherein L is a C2-C12 alkyl group optionally substituted with one ormore hydroxyl groups; n ranges from 0 to 10; and R1 is H or CH₃.
 16. Theoptical film of claim 11 wherein n is
 0. 17. The optical film of claim 1wherein the monomer is a mono(meth)acrylate monomer.
 18. The opticalfilm of claim 1 wherein the polymerizable resin composition comprisesone or more aromatic monomers or oligomers having at least two aromaticgroups and at least two (meth)acrylate groups.
 19. The optical film ofclaim 18 wherein the polymerizable resin comprises 25 wt-% to 75 wt-% ofthe aromatic monomers or oligomers having at least two aromatic groupsand at least two (meth)acrylate groups
 20. The optical film of claim 18wherein the aromatic monomer or oligomer having at least two aromaticgroups and at least two polymerizable (meth)acrylate groups has amolecular weight of at least 350 g/mole.
 21. The optical film of claim18 wherein the aromatic monomer or oligomer has the structure

wherein R1 is independently hydrogen or methyl; Z is independently—C(CH₃)₂—, —CH₂—, —C(O)—, —S—, —S(O)—, or —S(O)₂—; Q is independently Oor S; L is independently a C₂-C₆ alkyl group optionally substituted withone or more hydroxy groups; and and n ranges from 0 to
 10. 22. Theoptical film of claim 18 wherein the aromatic monomer or oligomer hasthe structure

wherein each R1 is independently H or methyl; each R2 is independentlyBr; m ranges from 0 to 4; each Q is independently O or S; n ranges from0 to 10; L is independently a C₂ to C₁₂ alkyl group optionallysubstituted with one or more hydroxyl groups; z is an aromatic ring; andt is independently 0 or
 1. 23. The optical film of claim 1 wherein thepolymerizable resin composition is non-halogenated.
 24. The optical filmof claim 1 wherein the optical film is a brightness enhancing filmhaving a single sheet gain of at least 1.59.
 25. The optical film ofclaim 1 wherein the polymerizable resin composition comprises inorganicnanoparticles. 26-31. (canceled)